Fluid-mediated partial alteration in monazite: the role of coupled dissolution–reprecipitation in element redistribution and mass transfer

Monazite [(Ce,LREE,Th,U,Ca)(P,Si)O₄], with complex zoning in Th and other elements, is commonly observed in metamorphic and igneous rocks. The hypothesis that this alteration is a product of fluid-mediated element mass transfer has been tested in the piston-cylinder press (CaF₂ assembly, cylindrical graphite oven) at 1,000 MPa and 900°C and in cold seal autoclaves on a hydrothermal line at 500 MPa and 600°C. Experiments included a relatively homogeneous monazite-(Ce) (7–8 wt% ThO₂) from a heavy mineral sand plus a series of alkali-bearing fluids including 2N NaOH, 2N KOH, and Na₂Si₂O₅ + H₂O. Experiments were conducted using BSE imaging, EMP analysis, and both TEM and HRTEM. A subset of monazite grains from each experiment show evidence of partial alteration in the form of areas enriched in Th + Si with sharp curvilinear compositional boundaries extending from the grain rim into the monazite interior. These ThSiO₄-enriched textures are similar to those commonly seen in natural examples of metasomatised monazite in both magmatic and metamorphic rocks. In the Na₂Si₂O₅ + H₂O experiments, scarce inclusions of britholite formed in the altered monazite. The altered monazite is also characterised by strong depletion in Pb, Ca, and Y. Thorium and Si mobility, coupled with the formation of britholite inclusions, during partial alteration in the monazite grain is considered to be the product of fluid-aided coupled dissolution–reprecipitation as opposed to solid-state diffusion. Since other fluids, including NaCl and KCl brines, do not result in the formation of these textures, the experimental replication of ThSiO₄-enriched areas in the monazite strongly suggests that similar textures in monazite observed in nature are fluid induced, specifically by alkali-bearing fluids. If true, complex metasomatically induced textures in monazite could yield information concerning the nature of the fluid responsible for their formation as well as allow for the dating of the metasomatic event, presuming that all the original radiogenic Pb has been removed.     

Evolution of acidity of hydrothermal fluids related to hydrolysis of chlorides

Composition of magmatogene fluids in respect of main components in a wide P-T range can be approximated by a system NaCl (± KCl)-CO₂-H₂O. The influence of H₂CO₃, H₃BO₃, H₂S and such rare component as NH₃ on fluids acidity appears to be insignificant. Therefore the acidity of supercritical fluids should be completely defined by dissociation constants of chloride hydrolysis products:

An experimental study of dissolution–reprecipitation in fluorapatite: fluid infiltration and the formation of monazite

In a series of timed experiments, monazite inclusions are induced to form in the Durango fluorapatite using 1 and 2 N HCl and H₂SO₄ solutions at temperatures of 300, 600, and 900°C and pressures of 500 and 1,000 MPa. The monazite inclusions form only in reacted areas, i.e. depleted in (Y+REE)+Si+Na+S+Cl. In the HCl experiments, the reaction front between the reacted and unreacted regions is sharp, whereas in the H₂SO₄ experiments it ranges from sharp to diffuse. In the 1 N HCl experiments, Ostwald ripening of the monazite inclusions took place both as a function of increased reaction time as well as increased temperature and pressure. Monazite growth was more sluggish in the H₂SO₄ experiments. Transmission electron microscopic (TEM) investigation of foils cut across the reaction boundary in a fluorapatite from the 1 N HCl experiment (600°C and 500 MPa) indicate that the reacted region along the reaction front is characterized by numerous, sub-parallel, 10–20 nm diameter nano-channels. TEM investigation of foils cut from a reacted region in a fluorapatite from the 1 N H₂SO₄ experiment at 900°C and 1,000 MPa indicates a pervasive nano-porosity, with the monazite inclusions being in direct contact with the surrounding fluorapatite. For either set of experiments, reacted areas in the fluorapatite are interpreted as replacement reactions, which proceed via a moving interface or reaction front associated with what is essentially a simultaneous dissolution–reprecipitation process. The formation of a micro- and nano-porosity in the metasomatised regions of the fluorapatite allows fluids to permeate the reacted areas. This permits rapid mass transfer in the form of fluid-aided diffusion of cations to and from the growing monazite inclusions. Nano-channels and nano-pores also serve as sites for nucleation and the subsequent growth of the monazite inclusions.     

Sodium-rich metasomatism in the upper mantle: Implications of experiments on the pyrolite-Na2O-rich fluid system at 950°C, 20 kbar

Sodium-rich metasomatism in the upper levels of the mantle has been modelled by reacting pyrolite with alkali-bearing H₂O fluids containing minor CO₂ and concentrations of Na₂O and Na₂O + K₂O (K/K + Na = 0.1 ) up to 4.0 g alkalies/10 g H₂O at 20 kbar and 950°C. With increasing alkali concentration, the amounts of amphibole (pargasite-edenite) and olivine increase as orthopyroxene and clinopyroxene decrease. Amphiboles show progressive increases in Na (and K) and Si concentrations and decreases in Al and Ca concentrations suggesting the dominant substitution mechanism is (Na, K) + SiAl + Ca. These results and least squares mass balance calculations suggest the reaction of clinopyroxene + orthopyroxene + spinel produces amphibole + olivine.In nature, upper mantle spinel lherzolite is commonly veined by a variety of rock types which may contain Ti-pargasite as a magmatic crystallization product. Pargasite-edenite occurs interstitially in spinel Iherzolite, often spatially related to Ti-pargasite and may be produced by hydrous fluids evolved during late stage crystallization of the veined rocks. This is supported by the close compositional correlation between the natural pargasite-edenite amphiboles and those produced in this study.The present study suggests that up to 43 wt.% amphibole may be accommodated in pyrolite in the presence of Na₂O-rich H₂O-CO₂ fluids. This represents 0.8 wt.% H₂O and 1.7 wt.% Na₂O in the hydrated pyrolite composition and indicates the importance of sodium in determining the extent of metasomatism. Sodium also lowers the solidus temperature of pyrolite by more than 50°C over the H₂O-saturated pyrolite system at 20 kbar.     

Thorium mineralization in hyperalkaline pegmatites and hydrothermalites of the Lovozero pluton,Kola Peninsula

The Lovozero pluton (Kola Peninsula, Russia) is an unique object from the standpoint of the abundance, diversity, and originality of Th mineralization. In contrast to other igneous rocks and to such chemical elements as Ca, REE, U, and Na, Th in the hyperalkaline pegmatites and hydrothermalites of the Lovozero pluton commonly occurs as its own mineral phases. Umbozerite Na₃Sr₄Th(Mn,Zn,Fe,Mg)[Si₈O₂₄](OH) (7 samples), Ti-Th silicate Na_0–7Sr_0–1ThTi_1–2Si₈O_22–23(OH) · nH₂O (8 samples), Na-Th silicate (Na,K)₄Th₃[Si₈(O,OH)₂₄] · nH₂O (6 samples), thorite (2 samples), steenstrupine-(Ce)-thorosteenstrupine series minerals (5 samples), and Th phosphate (Th,Na,K,Ca,Mg,U,Sr,Ba)[(P,Si, Al)₁O₄] · nH₂O (1 sample) were investigated in this study. Ti-Th silicates and Th phosphate have been described for the first time. All of the above-mentioned minerals have been examined with electron microprobe, IR spectroscopy, powder diffraction, thermogravimetric and optical methods. High-Th minerals such as steenstrupine, umbozerite, Th phosphate, and Na-Th silicates crystallized mainly during the ussingite stage of the pegmatite-forming process. At the early hydrothermal high-alkaline stage, steenstrupine was replaced with REE and Th aggregates (belovite, vitusite, seidite, Na-Th silicates, Ti-Th silicates, etc.). Thorite, Ti-Th silicates, and minerals of the rhabdophane and monazite groups were formed at the late hydrothermal low-alkaline stage. Despite the metamict features of almost all samples, stoichiometric ratios of cations in umbozerites and Ti-Th silicates remain stable. Clear relationships have been revealed between umbozerites and Ti-Th silicates, on the one hand, and seidite-(Ce), a Ti-silicate that has a zeolite-like structure, on the other. This implies that, under certain conditions, these minerals may be regarded as potential suppliers of Th to the environment due to the leaching of Th from zeolite channels.     

Uranium-rich accessory minerals in the peraluminous and perphosphorous Belvís de Monroy pluton (Iberian Variscan belt)

The strongly peraluminous, perphosphorous (<0.85 wt% P₂O₅) and low-Ca granites from the Belvís de Monroy pluton contain the most U-rich monazite-(Ce) and xenotime known in igneous rocks. Along with these accessory minerals, P-rich zircon occurs, reaching uncommon compositions particularly in the more fractionated units of this zoned pluton. Monazite displays a wide compositional variation of UO₂ (<23.13 wt%) and ThO₂ (<19.58 wt%), positively correlated with Ca, Si, P, Y and REE. Xenotime shows a high UO₂ content (2.37–13.34 wt%) with parallel increases of LREE, Ca and Si. Zircon contains comparatively much lower UO₂ (<1.53 wt%) but high P₂O₅ (<14.91 wt%), Al₂O₃ (<6.96 wt%), FeO (<2.93 wt%) and CaO (<2.24 wt%) contents. The main mechanism of incorporating large U and Th amounts in studied monazite and U in xenotime is the cheralite-type [(Th,U)⁴⁺ + Ca²⁺ = 2(Y,REE)³⁺] substitution. Zircon requires several coupled mechanisms to charge balance the P substitution, resulting in non-stoichiometric compositions with low analytical totals. Compositional variations in the studied accessory phases indicate that the substitution mechanisms during crystal growth depend on the availability of non-formula elements. The strong P-rich character of the studied granites increases monazite crystallization, triggering a progressive impoverishment in Th and LREE in the residual melts, and consequently increasing extraordinarily the U content in monazite and xenotime. This is in marked contrast to other peraluminous (I-type or P-poor S-type) granite series. The P-rich and low-Ca peraluminous melt inhibits uraninite crystallization, so contributing to the U availability for monazite and xenotime.     

Fluid inclusions in diamonds from the Diavik mine, Canada and the evolution of diamond-forming fluids

The analysis of micro-inclusions in fibrous diamonds from the Diavik mine, Canada revealed the presence of high density fluids (HDFs) that span a continuous compositional range between carbonatitic and saline end-members. The carbonatitic end-member is rich in Na, Ca, Mg, Fe, Ba and carbonate; the saline one is rich in K, Cl and water. In molar proportions, the composition of the saline end-member is: K₃₈Na_7.7Ca_1.8Mg_1.6Fe_1.5Ba_1.9SiO_3.1Cl₄₆(CO₃)_5.5(H₂O)₅₆ and that of the carbonatitic end member is: K₁₅Na₂₁Ca_6.7Mg_8.1Fe_6.2Ba_5.7Si_4.8Ti_1.4Al_1.9O₁₇Cl₂₉(CO₃)₂₉(H₂O)₂₉. The micro-inclusions in one diamond span a narrow range between a silicic end-member (rich in Si, K and water) and a carbonatitic one (rich in Mg, Ca, Fe and carbonate). Its average composition is: K₂₆Na_5.5Ca_13.8Mg_8.3Fe_9.6Ba_0.9P_2.5Si₂₅Ti_1.6Al_3.8Cl_2.5O₈₁(CO₃)₂₉(H₂O)₇₈. Thus, the Diavik diamonds span most of the known compositional range for fluids trapped in diamonds. Based on these data and previous analyses of fluids trapped in diamonds, we discuss possible models for the evolution of diamond-forming fluids. The most plausible model is where carbonatitic-HDFs are parental to all the other compositions. They evolve by fractionation of divalentions- and alkali-carbonates and by immiscible separation into saline- and silicic-HDFs. Each phase continues to evolve separately, crystallizing carbonates, diamond, and accessory silicates, phosphates, halides and more of the immiscible phase. Other processes, like the mixing of evolved fluids with fresh parental carbonatitic fluids, or metasomatic interactions with the wallrock also play a role in the evolution of the HDFs. We also propose that the parental carbonatitic-HDF evolves through fractional crystallization of an alkali-rich, low degree melt that is similar to the high pressure parental melts of kimberlites or lamproites.     

Cymrite as an indicator of high barium activity in the formation of hydrothermal rocks related to carbonatites of the Kola Peninsula

Cymrite, BaAl₂Si₂O₈ · nH₂O, is a rare mineral formed during low-grade dynamothermal metamorphism (T = 250–300°C, P = 1–3 kbar). Cymrite has been described from many metasedimentary ores and hydrothermal rocks. In carbonatites, it has been found for the first time. Cymrite has been identified in the Kovdor and Seblyavr massifs, Kola Peninsula. In Kovdor, this mineral has been described from one of the hydrothermal veins cutting the pyroxenite-melilitite-ijolite complex at the Phlogopite deposit; cymrite is associated with thomsonite, calcite, and stivensite. In the Seblyavr pluton, cymrite occurs in thin veins of calcite carbonatite that cut pyroxenite contacting with ijolite. Cymrite from the Seblyavr pluton is associated with calcite, natrolite, pyrite, and chalcopyrite. The mineral is optically negative and uniaxial, with extinction parallel to elongation; ω ～ 1.607(1). According to X-ray diffraction data, cymrite from Seblyavr is monoclinic, space group P1m1; unit-cell dimensions are: a = 5.33, b = 36.96, c = 7.66 Å, β = 90°, V = 1510.55 ų. According to the results of IR spectroscopy, in the series of samples from different massifs (in the running order Kovdor-Voishor-Seblyavr), the double-layer deformation is enhanced and accompanied by a decrease in the Si-O-Si angle and weakening of hydrogen bonds of interlayer water. The empirical formulas of cymrite calculated from electron microprobe analyses are Ba_0.93–0.95Ca_0.01–0.02K_0.00–0.05Na_0.02–0.04Al_1.97–2.01Si_1.99–2.03O₈(H₂O) and Ba_1.00–1.02Ca_0.00–0.01Sr_0.00–0.01Fe_0.00–0.01Al_1.94–2.00Si_1.98–2.03O₈(H₂O) at Seblyavr and Kovdor, respectively. Cymrite from the carbonatite massifs of the Kola Peninsula was formed under hydrothermal conditions at low temperature (200–300°C), high activity of Ba and Si, and high water pressure. At Kovdor, the mineral crystallized directly from the residual solution enriched in Ba. The sequence of mineral deposition is as follows: thomsonite-cymrite-calcite-stevensite. Cymrite from the Seblyavr pluton is a product of hydrothermal alteration of primary Na-K-Ba silicates of ijolite: nepheline, feldspar, and probably celsian. Natrolite replaces cymrite indicating high alkalinity of late hydrothermal fluids.     

Thermochemical study of natural montmorillonite

The paper reports results of an experimental thermochemical study (in a heat-flux Tian-Calvet microcalorimeter) of montmorillonite from (I) the Taganskoe and (II) Askanskoe deposits and (III) from the caldera of Uzon volcano, Kamchatka. The enthalpy of formation Δ _f H _el ⁰ (298.15 K) of dehydrated hydroxyl-bearing montmorillonite was determined by melt solution calorimetry: ?5677.6 ± 7.6 kJ/mol for Na_0.3Ca_0.1(Mg_0.4Al_1.6)[Si_3.9Al_0.1O₁₀](OH)₂ (I), ?5614.3 ± 7.0 kJ/mol for Na_0.4K_0.1(Ca_0.1Mg_0.3Al_1.5Fe _0.1 ³⁺ )[Si_3.9Al_0.1O₁₀](OH)₂ (II), ?5719 ± 11 kJ/mol for K_0.1Ca_0.2Mg_0.2(Mg_0.6Al_1.3Fe _0.1 ³⁺ ) [Si_3.7Al_0.3O10](OH)₂ (III), and ?6454 ± 11 kJ/mol for water-bearing montmorillonite (I) Na_0.3Ca_0.1(Mg_0.4Al_1.6)[Si_3.9Al_0.1O₁₀](OH)₂ · 2.6H₂O. The paper reports estimated enthalpy of formation for the smectite end members of the theoretical composition of K-, Na-, Mg-, and Ca-montmorillonite and experimental data on the enthalpy of dehydration (14 ± 2 kJ per mole of H₂O) and dehydroxylation (166 ± 10 kJ per mole of H₂O) for Na-montmorillonite.     

Formation of monazite and xenotime inclusions in fluorapatite megacrysts, Gloserheia Granite Pegmatite, Froland, Bamble Sector, southern Norway

Xenotime and monazite inclusions in fluorapatite megacrysts from a granitic pegmatite, Gloserheia, Froland, Bamble Sector, southern Norway are described utilizing high contrast backscattered electron imaging of cross sections of a selection of fluorapatite crystals. Electron microprobe analysis is then used to further characterize the xenotime and monazite, as well as (Y+REE) normal and depleted regions in the fluorapatite. In the (Y+REE) normal regions Y₂O₃ ranges from 0.4 to 1.3 whereas it ranges from below the electron microprobe detection limit to around 0.4 in the depleted regions. Low Y values in monazite (X_Y?=?0.01?0.05) co-existing with xenotime indicates that inclusion formation in the originally (Y+REE)-enriched fluorapatite must have occurred below 300°C. Formation of the xenotime and monazite inclusions is attributed to fluid-aided coupled dissolution-reprecipitation processes during the later stages of subsolidus cooling of the pegmatite. The fluorapatite megacrysts are hypothesized to have under gone two major fluid-induced alteration events. The first occurred sometime after crystallization was complete at temperatures below 300°C and resulted in the initial formation of the xenotime and monazite inclusions. The second occurred at some later time as the product of a relatively limited fluid infiltration, also under T?<?300°C. This resulted in the formation of (Y+REE)-depleted regions along lattice and cleavage planes while at the same time promoting Ostwald ripening of the xenotime inclusions resulting in larger grains in the (Y+REE)-depleted areas.     

Hydrogen-alkali exchange between silicate melts and two-phase aqueous mixtures: an experimental investigation

Experiments were performed in the three-phase system high-silica rhyolite melt + low-salinity aqueous vapor + hydrosaline brine, to investigate the exchange equilibria for hydrogen, potassium, and sodium in magmatic-hydrothermal systems at 800 °C and 100 MPa, and 850 °C and 50 MPa. The K ^aqm/melt _H,Na and K ^aqm/melt _H,K for hydrogen-sodium exchange between a vapor + brine mixture and a silicate melt are inversely proportional to the total chloride concentration (ΣCl) in the vapor + brine mixture indicating that HCl/NaCl and HCl/KCl are higher in the low-salinity aqueous vapor relative to high-salinity brine. The equilibrium constants for vapor/melt and brine/melt exchange were extracted from regressions of K ^{a q m / m e l t} _{H , N a} and K ^{a q m / m e l t} _{H , K} versus the proportion of aqueous vapor relative to brine in the aqueous mixture (F^aqv) at P and T, expressed as a function of ΣCl. No significant pressure effect on the empirically determined exchange constants was observed for the range of pressures investigated. Model equilibrium constants are: K ^aqv/melt _H,Na(vapor/melt)=26(±1.3) at 100 MPa (800 °C), and 19( ± 7.0) at 50 MPa (850 °C); K ^aqv/melt _H,K=14(±1.1) at 100 MPa (800 °C), and 24(±12) at 50 MPa (850 °C); K ^aqb/melt _H,b(brine/melt)= 1.6(±0.7) at 100 MPa (800 °C), and 3.9(±2.3) at 50 MPa (850 °C); and K ^aqb/melt _H,K=2.7(±1.2) at 100 MPa (800 °C) and 3.8(±2.3) at 50 MPa (850 °C). Values for K ^aqv/melt _H,K and K ^aqb/melt _H,K were used to calculate KCl/HCl in the aqueous vapor and brine as a function of melt aluminum saturation index (ASI: molar Al₂O₃/(K₂O+Na₂O+CaO) and pressure. The model log KCl/HCl values show that a change in melt ASI from peraluminous (ASI = 1.04) to moderately metaluminous (ASI = 1.01) shifts the cooling pathway (in temperature-log KCl/HCl space) of the aqueous vapor toward the andalusite+muscovite+K-feldspar reaction point. Received: 22 August 1996  / Accepted: 5 February 1997     

Thermodynamic Analysis of Secondary Minerals Stability in Altered Carbonatites of the Oldoinyo Lengai Volcano,Northern Tanzania

Carbonatites from the Oldoinyo Lengai volcano, northern Tanzania, are unstable under normal atmospheric conditions. Owing to carbonatite interaction with water, the major minerals—gregoryite Na₂(CO₃), nyerereite Na₂Ca(CO₃)₂, and sylvite KCl—are dissolved and replaced with secondary low-temperature minerals: thermonatrite Na₂(CO₃) · H₂O, trona Na₃(CO₃)(HCO₃) · 2H₂O, nahcolite Na(HCO₃), pirssonite Na₂Ca(CO₃)₂ · 2H₂O, calcite Ca(CO₃), and shortite Na₂Ca₂(CO₃)₃. Thermodynamic calculations show that the formation of secondary minerals in Oldoinyo Lengai carbonatites are controlled by the pH of the pore solution, H₂O and CO₂ fugacity, and the ratio of Ca and Na activity in the Na₂O–CaO–CO₂–H₂O system.     

On the stability of magmatic cordierite and new thermobarometric equations for cordierite-saturated liquids

In this work, we have reviewed a large compositional dataset (571 analyses) for natural and experimental glasses to understand the physico-chemical and compositional conditions of magmatic cordierite crystallization. Cordierite crystallizes in peraluminous liquids (A/CNK ≥1) at temperatures ≥750 °C, pressures ≤700 MPa, variable H₂O activity (0.1–1.0) and relatively low fO₂ conditions (≤NNO ? 0.5). In addition to A/CNK ratio ≥1, a required condition for cordierite crystallization is a Si + Al cation value of the rhyolite liquid of 4 p8O (i.e. calculated on the 8 oxygen anhydrous basis), which is consistent with low Fe³⁺ contents and the absence or low content of non-bridging oxygens (NBO). This geochemical condition is strongly supported by the rare, if not unique, structure of cordierite where the tetrahedral framework is composed almost exclusively of Si and Al cations the sum of which is equal to 4 p8O [i.e. (Mg,Fe)_8/9Al_16/9Si_20/9O₈], indicating that aluminium (and cordierite) saturation is limited by rhyolite liquids with Al = 4 ? Si. Indeed, synthetic or natural systems with Al > 4 ? Si always show metastable glass-in-glass separation or crystallization of refractory minerals such as corundum (Al_16/3O₈) and aluminosilicates (Al_16/5Si_8/5O₈). Multivariate regression analyses of literature data for experimental glasses coexisting with magmatic cordierite produced two empirical equations to independently calculate the T (±13 °C; ME, maximum error = 29 °C) and P (±16 %; ME% = 27 %) conditions of cordierite saturation. The greatest influence on the two equations is exerted by H₂O_melt and Al concentrations, respectively. Testing of these equations with other thermobarometric constraints (e.g. feldspar-liquid, GASP, Grt–Bt and Grt–Crd equilibria) and thermodynamic models (NCKFMASHTO and NCKFMASH systems) was successfully performed for Crd-bearing rhyolites and residual enclaves from San Vincenzo (Tuscany, Italy), Morococala Field (Bolivia) and El Hoyazo (Spain). The reliability of each calculated P–T pair was graphically evaluated using the minimum and maximum P–T–H₂O relationships for peraluminous rhyolite liquids modified after the metaluminous relationships in this work. Both P–T calculations and checking can be easily performed with the attached user-friendly spreadsheet (i.e. Crd-sat_TB).     

Experimental determination of magnesia and silica solubilities in graphite-saturated and redox-buffered high-pressure COH fluids in equilibrium with forsterite + enstatite and magnesite + enstatite

We experimentally investigated the dissolution of forsterite, enstatite and magnesite in graphite-saturated COH fluids, synthesized using a rocking piston cylinder apparatus at pressures from 1.0 to 2.1 GPa and temperatures from 700 to 1200 °C. Synthetic forsterite, enstatite, and nearly pure natural magnesite were used as starting materials. Redox conditions were buffered by Ni–NiO–H₂O (ΔFMQ = ??0.21 to ??1.01), employing a double-capsule setting. Fluids, binary H₂O–CO₂ mixtures at the P, T, and fO₂ conditions investigated, were generated from graphite, oxalic acid anhydrous (H₂C₂O₄) and water. Their dissolved solute loads were analyzed through an improved version of the cryogenic technique, which takes into account the complexities associated with the presence of CO₂-bearing fluids. The experimental data show that forsterite?+?enstatite solubility in H₂O–CO₂ fluids is higher compared to pure water, both in terms of dissolved silica (mSiO₂?=?1.24 mol/kg_H2O versus mSiO₂?=?0.22 mol/kg_H2O at P?=?1 GPa, T?=?800 °C) and magnesia (mMgO?=?1.08 mol/kg_H2O versus mMgO?=?0.28 mol/kg_H2O) probably due to the formation of organic C–Mg–Si complexes. Our experimental results show that at low temperature conditions, a graphite-saturated H₂O–CO₂ fluid interacting with a simplified model mantle composition, characterized by low MgO/SiO₂ ratios, would lead to the formation of significant amounts of enstatite if solute concentrations are equal, while at higher temperatures these fluid, characterized by MgO/SiO₂ ratios comparable with that of olivine, would be less effective in metasomatizing the surrounding rocks. However, the molality of COH fluids increases with pressure and temperature, and quintuplicates with respect to the carbon-free aqueous fluids. Therefore, the amount of fluid required to metasomatize the mantle decreases in the presence of carbon at high P–T conditions. COH fluids are thus effective carriers of C, Mg and Si in the mantle wedge up to the shallowest level of the upper mantle.     

Phase Chemistry Study of the Zabuye Salt Lake Brine: Isothermal Evaporation at 15°C and 25°C

Zabuye Salt Lake in Tibet, China is a carbonate-type salt lake, which has some unique characteristics that make it different from other types of salt lakes. The lake is at the latter period in its evolution and contains liquid and solid resources. Its brine is rich in Li, B, K and other useful minor elements that are of great economic value. We studied the concentration behavior of these elements and the crystallization paths of salts during isothermal evaporation of brine at 15°C and 25°C. The crystallization sequence of the primary salts from the brine at 25°C is halite (NaCl) → aphthitalite (3K2SO4·Na2SO4) → zabuyelite (Li2CO3)→ trona (Na2CO3·NaHCO3·2H2O) → thermonatrite (Na2CO3·H2O) → sylvite (KCl), while the sequence is halite (NaCl) → sylvite (KCl) → trona (Na2CO3·NaHCO3·2H2O) → zabuyelite (Li2CO3) → thermonatrite (Na2CO3·H2O) → aphthitalite (3K2SO4·Na2SO4) at 15°C. They are in accordance with the metastable phase diagram of the Na+, K+-Cl?, CO32?, SO42?-H2O quinary system at 25°C, except for Na2CO3·7H2O which is replaced by trona and thermonatrite. In the 25°C experiment, zabuyelite (Li2CO3) was precipitated in the early stage because Li2CO3 is supersaturated in the brine at 25°C, in contrast with that at 15°C, it precipitated in the later stage. Potash was precipitated in the middle and late stages in both experiments, while boron was concentrated in the early and middle stages and precipitated in the late stage.     

Fluid evolution in the Pote Shear Zone Harare-Shamva-Bindura greenstone belt (northeast Zimbabwe)

A fluid inclusion study was completed on syn-deformational quartz veins of the Pote River Shear Zone, which is situated on the border between the Harare-Bindura greenstone belt and the granitoids of the Chinamora Batholith. The fluid inclusions were studied by means of microthermometry and Laser-Raman microspectrometry. The fluid inclusions consist of three major compositional types: (1) H₂OCO₂±N₂±halite inclusions in clusters and trails; (2) H₂OCO₂ inclusions (H₂O = 30–60 vol. %) in trails; and (3) H₂O-halite inclusions in trails. These fluid generations are explained by trapping at different P-T conditions of two different fluids: a high salinity aqueous fluid and a low salinity H₂OCO₂ fluid with XH₂O around 0.8. High salinity aqueous fluid inclusions are characteristic for the granite-greenstone contact and are absent within the Harare-Shamva-Bindura greenstone belt. The high salinity aqueous fluid has, therefore, been interpreted as magmatic in origin. The low salinity H₂OCO₂ fluid is most likely metamorphic in origin.     

Dating metamorphic reactions and fluid flow: application to exhumation of high-P granulites in a crustal-scale shear zone, western Canadian Shield

The Legs Lake shear zone is a crustal‐scale thrust fault system in the western Canadian Shield that juxtaposes high‐pressure (1.0+ GPa) granulite facies rocks against shallow crustal (< 0.5 GPa) amphibolite facies rocks. Hangingwall decompression is characterized by breakdown of the peak assemblage Grt + Sil + Kfs + Pl + Qtz into the assemblage Grt + Crd + Bt ± Sil + Pl + Qtz. Similar felsic granulite occurs throughout the region, but retrograde cordierite is restricted to the immediate hangingwall of the shear zone. Textural observations, petrological analysis using P–T/P–M_H2O phase diagram sections, and in situ electron microprobe monazite geochronology suggest that decompression from peak conditions of 1.1 GPa, c. 800 °C involved several distinct stages under first dry and then hydrated conditions. Retrograde re‐equilibration occurred at 0.5–0.4 GPa, 550–650 °C. Morphology, X‐ray maps, and microprobe dates indicate several distinct monazite generations. Populations 1 and 2 are relatively high yttrium (Y) monazite that grew at 2.55–2.50 Ga and correspond to an early granulite facies event. Population 3 represents episodic growth of low Y monazite between 2.50 and 2.15 Ga whose general significance is still unclear. Population 4 reflects low Y monazite growth at 1.9 Ga, which corresponds to the youngest period of high‐pressure metamorphism. Finally, population 5 is restricted to the hydrous retrograded granulite and represents high Y monazite growth at 1.85 Ga that is linked directly to the synkinematic garnet‐consuming hydration reaction (KFMASH): Grt + Kfs + H₂O = Bt + Sil + Qtz. Two samples yield weighted mean microprobe dates for this population of 1853 ± 15 and 1851 ± 9 Ma, respectively. Subsequent xenotime growth correlates with the reaction: Grt + Sil + Qtz + H₂O = Crd. We suggest that the shear zone acted as a channel for fluid produced by dehydration of metasediments in the underthrust domain.     

Monazite-Xenotime-Garnet Equilibrium in Metapelites and a New Monazite-Garnet Thermometer

Prograde suites of pelitic rocks were examined with electronmicroprobe and laser ablation inductively coupled plasma massspectrometry to determine the systematics of element partitioningbetween coexisting monazite, xenotime, and garnet. Monazitegrains that grew in equilibrium with xenotime are enriched inY and Dy compared with monazite that grew in xenotime-absentassemblages. Y and heavy rare earth element contents of monazitecoexisting with xenotime increase with rising temperature. Monazite–xenotimeY–Gd and Y–Dy partitioning is systematic withina metamorphic grade, and increases slightly with increasingmetamorphic grade, suggesting that monazite–xenotime pairsapproached partitioning equilibrium. Garnet and monazite inboth xenotime-bearing and xenotime-absent assemblages show astrong ( R² = 0·94) systematic relationship between inversetemperature and ln(K_Eq) for the net-transfer equilibrium YAG+ OH-Ap + (25/4)Qtz = (5/4)Grs + (5/4)An + 3YPO₄-Mnz + 1/2H₂O,suggesting that garnet and monazite crystallized in compositionalequilibrium. The following temperature–K_Eq relationshipfor the equilibrium above has been derived:      

Experimental study of natural pyrochlore and niobium oxide solubility in Alkaline hydrothermal solutions

The concentration and temperature dependences of pyrochlore and Nb oxide solubility in Na₂CO₃ and Na₂СO₃ + NaF aqueous solutions with concentrations from 0.01 to 2.0 m at 300–550°C and 50 and 100 MPa (the Co–CoO buffer) are studied. It is established that the Nb equilibrium content in the solution increases at 550°C and 100 MPa with an increase in mNa₂CO₃ and reaches the value of 10^–4 m. The Nb₂O₅ solubility almost does not change as the concentration of Na₂CO₃ increases and is found within 10^–6 to 10^–5.5 m.     

Monazite–xenotime miscibility gap thermometry. I. An empirical calibration

Rare earth element (REE) and yttrium concentrations of coexisting monazite and xenotime were determined from a suite of seven metapelites from the Variscan fold belt in NE Bavaria, Germany. The metapelites include a continuous prograde, mainly low-P (3–5 kbar) metamorphic profile from greenschist (c. 400 °C) to lower granulite facies conditions (c. 700 °C). The LREE (La–Sm) are incorporated preferentially in monoclinic monazite (REO₉ polyhedron), whereas the HREE plus Y are concentrated in tetragonal xenotime (REO₈ polyhedron). The major element concentrations of both phases in all rocks are very similar and do not depend on metamorphic grade. Monazite consists mainly of La, Ce and Nd (La_0.20–0.23, Ce_0.41–0.45, Nd_0.15–0.18)PO₄, all other elements are below 6 mol%. Likewise, xenotime consists mainly of YPO₄ with some Dy and Gd solid solutions (Y_0.76–0.80, Dy_0.05–0.07, Gd_0.04–0.06). In contrast, the minor HREE concentrations in monazite increase strongly with increasing metamorphic grade: Y, Dy and Gd increase by a factor of 3–5 from greenschist to granulite facies rocks. Monazite crystals often show zonation with cores low in HREE and rims high in HREE that is interpreted as growth zonation attained during prograde metamorphism. Similarly, Sm and Nd in xenotimes increase by a factor of 3–4 with increasing metamorphic grade. Prograde zonation in single crystals of xenotime was not observed. The X_HREE+Y in monazite and X_LREE in xenotime of the seven rocks define two limbs along the strongly asymmetric miscibility gap from c. 400 °C to 700 °C. The empirical calibration of the monazite miscibility gap limb coexisting with xenotime is appropriate for geothermometry. Due to its contents of U and Th, monazite has often been used for U–Pb age determination. The combination of our empirical thermometer on prograde zoned monazite along with possible age determination of zoned single crystals may provide information about prograde branches of temperature–time paths.